An efficient method for synthesis of some heterocyclic compounds containing 3-iminoisatin and 1,2,4-triazole using Fe3O4 magnetic nanoparticles

1,2,4-triazole derivatives were prepared by reaction of thiocarbohydrazide and some esters in 60% ethanol. Condensation of 1,2,4-triazole derivatives with isatin gave Schiff bases of 3-iminoisatin derivatives. Reaction of malonic or succinic acid dihydrazide with isatin lead to formation of N,N'-bis-(3-imino-1,3-dihydro-indolyl-2-one)-malonamide 8a and N,N'-bis-(3-imino-1,3-dihydro-indolyl-2-one)succinamide 8b in good yields under mild reaction conditions. These reactions are catalyzed by Fe₃O₄ MNPs. The chemical structures were confirmed by Fourier transform-infrared, ¹H-NMR, ¹³C-NMR, gas chromatography-mass spectrometry spectroscopy, and elemental analysis.     

LIQUID-LIQUID EXTRACTION STUDIES OF METAL IONS WITH DIAZACROWN AND STRUCTURE ANALOGOUS OPEN-CHAIN COMPOUNOS

1,10-diaze [8]crown-6, their N,N'-dibutyl- and dioctyl-substituted derivatives and the structure analogous open-chein tetreoxedieza slkanee have been synthesized in order to examine the extraction properties for Na⁺, K⁺, Sr²⁺ and Hg²⁺. It wes found, that the extraction of strontium, potassium and sodium picratee with azacrown compounds ie much higher than that with open-chein oxaaze alkanes. 1,10-diaze [18] erown-6 has a good selectivity for the extraction of Sr²⁺ over K⁺ and Na in alkaline solution. In the case of Sr²⁺ the diffarencea between tha various azacrown compounds are email, whereea in the caee of K⁺ and Na the substituted derivativee are better extractante. Theserssulte correspond qualitativsly with tha order of stebility conetantB in protic solvsnts. The extrectebility of N,N'-dioctyl-l, 10-dieze[18]crown-6 for HgCl₂ is very high. Contrerv to the order of stability conetants the uneubetituted conpound do not extract mercury under the choeen experimental condition*. The extraction power of open-chain conpounde ie aleo high and strong Influenced by the alkyl eubatltuente at the nitrogen donor stons,     

Darstellung und eigenschaften eines ionenaustauschers mit einem 1,3-diketon als Ankergruppe auf der Basis von Polystyrol

Aminopolystyrene is reacted with diketene to an exchanger with 1,3-diketone as anchor group. The capacity for Fe³⁺ ions is 3.2 mmol/g. The exchange comprises a fast and a slow step. The distribution coefficients for UO, Cu²⁺, Ni²⁺ and Fe³⁺ ions are presented as function of pH.     

Synthesis and properties of a cellulose exchanger with the crown ether diaminodibenzo-17-crown-5 as anchor group

A new cellulose exchanger was synthesized from “o-aminophenolcellulose” by diazotation and coupling with diaminodibenzo-17-crown-5. The distribution coefficients for Ca²⁺, Sr²⁺, Ba²⁺, Na⁺ and K⁺ were determined in water/methanol mixtures as a function of the water content. Separation of Ca²⁺, Na⁺ and K⁺ and fractionation of the calcium isotopes ⁴⁸Ca and ⁴⁰Ca were investigated. The enrichment factor ε = 4.9 · 10^?3 for ⁴⁸Ca²⁺ is appreciably higher than that found for cation exchange resins with ? SO₃H groups, but lower than that reported for certain cryptands.     

Structure and Properties Relationships of Epoxy Resins Part 1: Crosslink Density of Cured Resin: (II) Model Networks Properties

Carefully designed resin precursors of high purity, viz. N,N-bis-(2,3-epoxypropyl)-N',N-dimethyl-4,4′-diaminodiphenylenemethane (G2A) and N,N-bis-(2,3-epoxypropyl)-N,N-dimethyl-4,4′-diamino-diphenylenemethane (G2S) were used in combination with N,N,N',N-tetrakis-(2,3-epoxypropyl)-4,4′-diaminodiphenylene methane, TGDDM, and cured with stoichiometric amounts of 4,4′-diamino-diphenylene methane (DDM) to produce networks with a range of controlled crosslink density. The tensile moduli E of the networks in the rubbery state, at T_g+30°C, T_g+45°C and T_g+60°C, were measured using a thermal mechanical analyser. Using the statistical theory of rubber elasticity and the observed values of E, the number average molecular weights between crosslink points M_c for the cured resins were deduced. The experimental M_c values were then compared with those derived by calculations based on a probabilistic model of the network proposed by Chu and Seferis.¹ The experimental M_c values were 2.5 to 5.5 times larger than the calculated ones. The differences were attributable to a consumption of only 40% of the available secondary amino hydrogen via epoxy-amine reaction. A direct relationship was established between the glass transition temperature and the crosslink density 1/M_c for the resins, and the dynamic mechanical properties were studied. The thermal stability of cured resins studied by thermo-gravimetric analysis indicated an enhancement of stability as 1/M_c was reduced. The amount of water absorbed by cured resin was directly proportional to 1/M_c.     

Polystyrolaustauscher mit 5-(4-dimethylaminobenzyliden)-rhodanin als ankergruppe für die abtrennung von silber,gold und quecksilber

The distribution coefficients of Ag⁺, Au³⁺, and Hg²⁺ on a polystyrene exchanger with 5-(4-dimethylaminobenzylidene)-rhodanin as anchor group are determined as function of pH in 0,1 M NaNO₃ as basic solution and after addition of NaCl, NH₄NO₃, Na₂S₂O₃ or NaCN. Ag⁺ ions are bound with relatively high distribution coefficients if the concentrations of NaCl, NH₄NO₃ and NaCN are low. Na₂S₂O₃ interferes even in low concentrations. Au³⁺ and Hg²⁺ ions are bound with relatively high distribution coefficients in the presence of 0.5 M NaCl.     

Highly porous,water-swellable,and reusable chelating polymeric gels for heavy metal ion removal from aqueous waste

Sequestration and removal of heavy metal ions from aqueous solutions pose multiple challenges. Ease of synthesis, high adsorption capacity and ease of regeneration are important considerations in the design of polymeric adsorbent materials developed for this purpose. To meet this objective, a new approach was used to design and synthesize a highly porous polystyrene-based resin (IDASR15) bearing iminodiacetate functional groups in every repeat unit by free radical polymerization with N, N'-methylenebisacrylamide as crosslinker followed by base hydrolysis. The physiochemical chemical properties of the resin were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, equilibrium swelling value (ESV) and thermogravimetric analysis. Metal uptake capacity of IDASR15 towards low concentrations of various toxic heavy metal ions such as Cu²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Co³⁺, Cr³⁺, Fe²⁺, Fe³⁺, and Al³⁺ were investigated from their aqueous solution by batch method and found to be 0.943–2.802 mmol/g. The maximum capacity was 2.802 mmol/g obtained for Cu²⁺ ion at pH 5. The potential for regeneration and reuse has been demonstrated with Cu²⁺ ion by batch and column methods. The reported results suggest that IDASR15 is a highly efficient and porous complexing agent for commonly found toxic metal ions in aqueous streams with a high ESV of 68.55 g of water/1.0 g of IDASR15. It could also be reused ~99.5% of adsorption efficiency which is very promising and holds significant potential for waste-water treatment applications.     

Design and synthesis of novel fluorescence sensing perylene diimides based on photoinduced electron transfer

Two novel tetraester- and PAMAM-branched perylene diimides were synthesized and configured as “fluorophore-spacer-receptor” systems based on photoinduced electron transfer. Due to their long alkylester and alkylamine terminal groups the examined compounds were well soluble in organic solvents. Photophysical characteristics of the dyes were investigated in DMF and water/DMF (1:1, v/v) solution. The ability of the synthesized perylene diimides to detect cations was evaluated by the changes in their fluorescence intensity in the presence of metal ions (Zn²⁺, Co²⁺, Cu²⁺, Fe³⁺, Pb²⁺, Hg²⁺, Ag⁺ and Ni²⁺) and protons. The dyes under study displayed “off–on” switching in its fluorescence as a function of pH, which is attributed to disallowing photoinduced electron transfer from the receptor moiety to the fluorophore. PAMAM-branched dye displayed a good pH sensor activity (FE = 6.4), however the pH sensing ability of tetraester was substantially higher (FE = 184). In the presence of Cu²⁺ and Pb²⁺ ions tetraester quenched its fluorescence intensity (FQ = 22 and 12 respectively), while PAMAM-branched dye enhanced its fluorescence intensity with pronounced selectivity to Cu²⁺ and Fe³⁺ (FE = 3.2 and 4.9, respectively). The results obtained indicate the potential of the novel compounds as fluorescent detectors for metal ions with pronounced selectivity towards Cu²⁺, Pb²⁺ and Fe³⁺ ions and highly efficient “off–on” pH switches, especially a tetraester-branched perylene diimide.     

Removal of Co, Cs, and Zr radioisotopes from aqueous solutions using cellulose iminodiacetic acid chelating cum cation-exchanger

The iminodiacetic acid group containing resin acts as a chelating ion exchanger as well as a weakly acidic cation exchanger, depending upon the species present in the solution. Iminodiacetic acid group has been incorporated onto cellulose by a modified Porath's method of functionalization of polysaccharides. The resin has been used for removal of ⁵⁸Co, ¹³⁴Cs, and ⁹⁵Zr radioisotopes from their separate aqueous solutions. ⁹⁵Zr as [Zr(OH)₂(H₂O)₄]⁸⁺ tetrameric species is adsorbed from the aqueous solution at low pH through cation exchange cum chelate formation. ⁵⁸Co as Co²⁺ is complexed with the resin. ¹³⁴Cs as Cs⁺ is exchanged with equivalent amount of H⁺ ions. Cs⁺ was eluted from resin using 0.3N HCl, Co²⁺ with 4N HCl and Zr(IV) with 5N HCl. Final disposal of the resin can be done by encapsulation in the cement concrete.     

Characterization and adsorption behavior of newly synthesized sodium bis(2-ethylhexyl) sulfosuccinate–cerium (IV) phosphate (AOT–CeP) cation exchanger

A new cationic exchange material, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with cerium (IV) phosphate (AOT–CeP) has been synthesized. The characterization of the ion exchanger was performed by using infra red spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTA/DTG) and elemental analysis. The ion exchange properties like ion exchange capacity, elution and concentration behavior of AOT–CeP were determined by taking the material into a column and elution of H⁺ was done by NaNO₃. The thermal stability of the ion exchanger was studied by determining ion exchange capacity after heating to different temperatures for one hour. The adsorption studies on AOT–CeP demonstrated that the material is selective for Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions. AOT–CeP was found to be effective for the separation of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of alkali metals/alkaline earth metals. This cationic exchanger was also effective for the removal of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of acid and other transition metal ions. Thus, AOT–CeP can be used for the removal of these ions from the waste water during its treatment.     

Novel 4-(2,2,6,6-tetramethylpiperidin-4-ylamino)-1,8-naphthalimide based yellow-green emitting fluorescence sensors for transition metal ions and protons

Two novel yellow-green emitting 1,8-naphthalimides, containing a 4-amino-2,2,6,6-tetramethylpiperidinyl moiety, were configured as “fluorophore–spacer–receptor” systems. The photophysical characteristics of the dyes were investigated in both DMF and water/DMF (4:1, v/v) solutions. The ability of the new compounds to detect cations was evaluated by means of the changes in their fluorescence intensity imparted by the presence of transition metal ions (Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺) and protons. The presence of metal ions and protons was found to disallow photoinduced electron transfer resulting in enhanced fluorescence intensity. The results clearly show that only Cu²⁺ ions and protons were effectively detected, indicating the potential of the novel compounds as highly efficient “off–on” switchers for Cu²⁺ ions and protons.     

Poly(amide thioether)s by addition of ethanedithiol to diallylamides

The preparation of poly(amide thioether)s by addition of ethanedithiol to diallylamides in the presence or absence of peroxide catalysts is reported for the first time. Diallylamide monomers N,N'-diallyloxalamide, N,N'-diallylmalonamide and N,N'-diallylterephthalamide have been prepared by aminolysis of the corresponding esters with allylamine. The structures of the resulting polymers have been elucidated by elemental microanalysis and ¹H NMR and IR spectroscopy. The polymers obtained both as Markovnikov and anti-Markovnikov types of addition are highly crystalline compounds.     

PART 3. THE EXTRACTION OF Co2+, Ni2+, Cu2+ AND Zn2+ USING NOVEL DITERTIARY-AMINEEXTRACTANTS

The syntheses of N-N-octyl-2-2'-pyridylimidazole and N,N'-di-n-octyl-(a)-aminopicoline are presented. Their extraction properties are compared with that of an aliphatic diamine N,N,N',N'-tetraoctylethylene-diamine. The reagents, dissolved in chloroform, were used to extract divalent cobalt, nickel, copper and zinc from aqueous chloride medium. Two extraction mechanisms are postulated for the extraction of these metals, and extraction data are discussed in terms of these postulates.

Extraction of the copper(II) ion at low pH values with amines is best effected by the inclusion of aromatic nitrogen atoms into a diamine extractant.     

Radiative and Nonradiative Decay of Electronically Excited HNF and DNF

Decay lifetimes for a range of HNF and DNF levels in their excited à ²A' electronic states, in specific K' stacks and in some cases in individual N' rotational levels, are reported. Above a threshold energy, these lifetimes are found to drop, in a K'- and N'-dependent way, below the extrapolated purely radiative lifetimes. This reduction in lifetime is ascribed to the onset of nonradiative, predissociative decay. Lifetimes for individual N' rotational levels in the HNF(òA') (0,4,0) and DNF(òA') (0,6,0) vibrational manifolds are also reported. These are found to fluctuate in a seemingly random manner vs. N', reflecting the variation of the coupling to the dissociation continuum. The implications of these results and, from other experiments, the direct observation of NH(X³Σ⁻) and ND(X³Σ⁻) photofragments for the dynamics of the nonradiative decay of electronically excited HNF and DNF are discussed.     

Synthesis and Properties of Two Amino Carboxylic Acid Gemini Surfactants

The number of hydrophilic and hydrophobic groups of a surfactant has a great influence on its property. Two Gemini surfactants, N,N″‘-didodecyl-N,N',N″,N″‘-tetrapropionate triethylenetetramine and N,N'-didodecyl-N,N'-dipropionate ethylenediamine (referred as DTPTT and DDPED), were prepared by Michael addition reaction of the didodecyl secondary amines with methyl acrylate. The didodecyl secondary amines were synthesized by nucleophilic substitution reaction of triethylenetetramine or ethylenediamine with bromododecane. The DTPTT and DDPED surfactants were characterized by mass spectrometry and proton nuclear magnetic resonance spectrometry. The surface activities of the DTPTT and DDPED aqueous solutions were studied by surface tension measurements. The surface tension and critical micelle concentration (cmc) of DDPED is smaller than that of DTPTT. The DDPED can reduce the surface tension of water to approximate 34 mN m⁻¹ at concentration levels of 10⁻⁵ mol L⁻¹. The aggregation behavior of the DTPTT and DDPED aqueous solution were studied by dynamic light scattering and transmission electron microscopy. Both surfactants can form spherical vesicles at a solution of about 3–5 times cmc of the Gemini surfactants. The foam property was determined by nitrogen blowing method. The DTPTT has relatively good foaming ability and DDPED has excellent foam stability. The foam volume of DDPED barely change within 1000s. The emulsion stability of the Gemini surfactants was determined by separation time of water from the emulsion. The emulsion stability of DDPED is equivalent to Tween 80. The DDPED Gemini surfactant with two hydrophilic carboxylic groups has better surface activity, foam stability, and can be used as an O/W emulsifier.     

Sorption behavior of ion-exchange terpolymer resin with environmental impact: synthesis,characterization and isotherm models

A novel terpolymer acts as an effective chelating ion exchanger which was synthesized using 2-amino-6-nitro-benzothiazole and semicarbazide with formaldehyde (BSF) by solution condensation technique. Its ion exchange properties was determined against certain metal ions viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ using batch equilibrium technique with different electrolyte concentrations, pH ranges and time intervals. The results of batch studies revealed that the separation of the selected metal ions from the aqueous solution by the terpolymer is found to be excellent compared to the available commercial resins and earlier reported resins. The order of metal ion uptake at higher concentrations by the BSF terpolymer at lower pH is Cu²⁺ > Ni²⁺ > Fe³⁺ and at lower concentration at higher pH is Zn²⁺ > Co²⁺ > Pb²⁺. The reusability of the resin was also reported for its effective ion-exchange behaviour for several cycles. The adsorption isotherm model was evaluated and the results are in good agreement with each other. The order of kinetics was also determined and the resin follows pseudo-second-order kinetics. Moreover, the physico-chemical analysis gives strong evidence for the effective metal ion removal compared with the earlier reported and commercial resins. Earlier, the structure and the properties of the synthesized novel chelating resin were clearly elucidated by elemental, FTIR, UV–Vis, ¹H & ¹³C NMR spectra, GPC, SEM and XRD.     

Modeling of Sorption Dynamics in Transition Metal Ion–Weak-Base Ion Exchanger Systems in Terms of Surface Complexation Theory

A model is constructed for sorption dynamics in multicomponent ion-exchange systems with a weak-base ion exchanger. The model is based on computer-solved nonlinear material balances and internal-diffusion kinetic equations. The multicomponent equilibria involving a weak-base ion exchanger are described in terms of surface complexation theory. According to this theory, the fixed amino groups of the ion exchanger (Lewis bases) and sorbate anions form complexes with metal cations (Lewis acids). These complexes are located in different Stern layers at different distances from the surface. Sorption dynamics models are considered for the frontal ion-exchange chromatographic separation of the H⁺/A/B/X (A, B; = Cu²⁺, Zn²⁺, Ni²⁺, Cd²⁺; X = Cl^–, SO ₄ ^2– ) systems on the amino-containing weak-base ion exchangers Purolite A-109 and Fuji PEI-CS-07. Frontal ion-exchange chromatograms are compared for a number of multicomponent systems.     

A novel DNA light switch [Ru(bpy)2pzip]2+ activated by cobalt(II) ion

A novel ruthenium(II) complex, [Ru(bpy)₂pzip]²⁺ has been synthesized and characterized. The DNA-binding properties of this complex have been studied by spectroscopic and viscosity measurements. The results indicated that the complex [Ru(bpy)₂pzip]²⁺ bound to double-stranded DNA in an intercalation mode. In the presence of Co²⁺, the emission of DNA–[Ru(bpy)₂pzip]²⁺ can be quenched. And when EDTA was added, the emission was recovered. The experiment results show that [Ru(bpy)₂pzip]²⁺ exhibited the “on–off–on” properties of molecular “light switch”.     

Synthesis of a novel inorganic cation exchanger based on molybdate: Applications for removal of Pb2+, Fe3+ and Mn2+ ions from polluted water

A novel manganese phosphomolybdate exchanger was synthesized, dried at different temperatures, and evaluated for the elimination of lead, iron, and manganese ions from aqueous solutions. The chemical structure of the cation exchanger was established using Fourier-transform infrared, scanning electron microscopy, Thermo gravimetric analysis/ Differential thermal analysis, and X-ray diffraction. The adsorption performance of the heavy metals Pb²⁺, Fe³⁺, and Mn²⁺ toward the synthesized material has been studied. The obtained outcomes show that the selectivity of the cationic exchanger was descending in this order, Pb²⁺ > Fe³⁺ > Mn²⁺. The highest adsorption capacity was shown to be decreased as drying temperature of the exchanger increases from 50°C to 800°C.     

A novel water soluble octaazamacrocyclic dinuclear copper(II) complex with tetra-pendant arms: Crystal structure and SOD activity

A novel water-soluble octaazamacrocyclic dinuclear copper(II) complex with tetra-pendant arms, [Cu₂L] Cl₂? 5H₂O, was synthesized by [2+2] condensation between 2, 6-diformyl-4-chlorophenol and N, N, N', N'-tetrakis(2'-aminoethyl)-1, 2-diaminopropane in the presence of Cu(OAc)₂·H₂O. Single-crystal X-ray structural analysis reveals that every copper(II) adopts a trigonal bipyramid coordination configuration. Macrocyclic units are joined together by strong π–π stacking interaction with centroid–centroid distance of 3.658 Å. Water pentamers with O–O distances of 2.099–2.841 Å are observed in the complex. The activity of superoxide dismutase of the complex has been investigated by the nitro blue tetrazolium method.